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971.
Nakano S Karimata H Ohmichi T Kawakami J Sugimoto N 《Journal of the American Chemical Society》2004,126(44):14330-14331
The thermodynamics of DNA duplex structures in the presence of high concentrations of cosolutes in solution were investigated to discern nucleic acid structures and functions in living cells. In the presence of ethylene glycol (EG) and poly(ethylene glycol) (PEG) (MW = 200-8000), the stability of the oligomer DNA duplexes with differing nucleotide length varied, depending on the nucleotide length as well as the size of PEG. It was also revealed that the decrease of water activity is the primary factor for destabilization of the short (8-mer) duplex by addition of high molecular weight PEGs as well as low molecular weight PEGs and other low molecular weight cosolutes. In addition, the number of water molecules taken up per base pair formation was the same for all the PEGs and for 1,2-dimethoxyethane, which was greater than in the cases of glycerol, EG, 1,3-propanediol, and 2-methoxyethanol, suggesting that the solvation of nucleotides may differ, depending on the cosolute structure. These findings are useful not only for understanding nucleic acid structures and functions in cells but also for the design of oligonucleotides applicable for cells, such as antisense nucleic acids, RNAi, and DNA chips. 相似文献
972.
T Matumoto T A Iinuma T Ishikawa Y Tateno N Kosaka Y Okada K Makita J Nishikawa K Machida M Iio 《Radioisotopes》1985,34(9):486-492
The purpose of this study is to evaluate the clinical efficacy of liver SPECT (single photon emission computed tomography). The two examinations were performed in 76 cases with SOL (space occupying lesion) and 58 normal cases. The results of the image reading by the planar image only (PS) and that of the image reading by the combination of PS and SPECT (PS + SPECT) were analyzed by ROC (receiver operating characteristic) analysis. The ROC curves showed that SPECT appears to reduce the number of results which were equivocal by the image reading of PS only. The detectability of SPECT for SOL in the left lobe of liver was less than that of PS without statistical significance. However, the performance of SPECT for SOL in the right lobe of liver was significantly better than that of PS. 相似文献
973.
Juliana Canto Duarte Rita de Cássia Silva Luz Flavio Santos Damos Adriano Bof de Oliveira Lauro Tatsuo Kubota 《Journal of Solid State Electrochemistry》2007,11(5):631-638
The electrocatalytical oxidation of hydrazine at low potential using tetracyanoquinodimethanide adsorbed on silica modified
with titanium oxide was investigated by cyclic voltammetry and amperometry. The modified electrode was prepared modifying
a carbon paste electrode employing lithium tetracyanoquinodimethanide adsorbed onto silica gel modified with titanium oxide.
This electrode showed an excellent catalytic activity and stability for hydrazine oxidation. With this modified electrode,
the oxidation potential of hydrazine was shifted toward less positive value, presenting a peak current much higher than those
observed on a bare GC electrode. The linear response range, sensitivity and detection limit were, respectively, 2 up to 100 μmol
l−1, 0.36 μA l μmol−1, and 0.60 μmol l−1. The repeatability of the modified electrode evaluated in term of relative standard deviation was 4.2% for 10 measurements
of 100 μmol l−1 hydrazine solution. The number of electrons involved in hydrazine oxidation (4), the heterogenous electron transfer rate
constant (1.08 × 103 mol−1 l s−1), and diffusion coefficient (5.9 × 10−6 cm2 s−1) were evaluated with a rotating disk electrode. 相似文献
974.
Minami T Okauchi T Matsuki H Nakamura M Ichikawa J Ishida M 《The Journal of organic chemistry》1996,61(23):8132-8140
Phosphonoketene dithioacetals 3a-e were obtained in good yields by the reaction of ethyl phosphonoacetates 1a,b with 2-4 equiv of thiols 2a-c in the presence of an alkylaluminum dichloride or dialkylaluminum chlorides. Reaction of 2,2-dithio-1-phosphonovinyl anions with aldehydes afforded allylic alcohols 4-7, 11-18 in good to moderate yields. Treatment of the alcohols 4-6 with t-BuOK in THF led to symmetrical [2 + 2] cycloadducts 20-22 of 1,1-(ethylenedithio)allenes in moderate yields, while a similar reaction of the alcohols 11-13 produced a mixture of symmetrical and unsymmetrical [2 + 2] cycloadducts of 1,1-(trimethylenedithio)allenes,23a-25a and 23b-25b, in 55-94% yields. The alcohol 15 on a similar treatment gave 3-tert-butyl-1,1-bis(ethylthio)allene (26) in quantitative yield. The structures of 20 and 23b were determined by X-ray analysis. Treatment of the alcohols 15 and 18 with trifluoromethanesulfonic acid/n-Bu(4)NX (X = Br, I) or triphenylphosphine/CBr(4) in CH(2)Cl(2) afforded alpha-phosphonodithioacryclic acid esters 34 and 35 in 25-52% yields. The tandem Michael-Wittig reaction of 35 with sodium salt of 2-pyrrolecarbaldehyde in DMF gave ethyl 3-phenyl-3H-cyclopenta[a]pyrrole-2-dithiocarboxylate (36) in 25% yield. 相似文献
975.
Ishiyama T Nobuta Y Hartwig JF Miyaura N 《Chemical communications (Cambridge, England)》2003,(23):2924-2925
Aromatic C-H borylation of arenes and heteroarenes using stoichiometric amounts of pinacolborane was catalyzed by an iridium complex generated from 1/2[Ir(OMe)(COD)]2 and 4,4'-di-tert-butyl-2,2'-bipyridine at room temperature in hexane and afforded the corresponding aryl- and heteroarylboronates in high yields with excellent regioselectivities. 相似文献
976.
The reduction of 4-nitrophenol (4-NP) has been carried out on a modified glassy carbon electrode using cyclic and differential pulse voltammetry (DPV). The sensor was prepared by modifying the electrode with lithium tetracyanoethylenide (LiTCNE) and poly-l-lysine (PLL) film. With this modified electrode 4-NP was reduced at −0.7 V versus SCE. The sensor presented better performance in 0.1 mol l−1 acetate buffer at pH 4.0. The other experimental parameters, such as concentration of LiTCNE and PLL, pulse amplitude and scan rate were optimized. Under optimized operational conditions, a linear response range from 27 up to 23200 nmol l−1 was obtained with a sensitivity of 3.057 nA l nmol−1 cm−2. The detection limit for 4-NP determination was 7.5 nmol l−1. The proposed sensor presented good repeatability, evaluated in term of relative standard deviation (R.S.D.=4.4%) for n=10 and was applied for 4-NP determination in water samples. The average recovery for these samples was 103.0 (± 0.7)%. 相似文献
977.
Kazuaki Ito Haruki Shimazu Eiji Shoto Mitsumasa Okada Takeshi Hirokawa Hiroshi Sunahara 《Journal of chromatography. A》1994,670(1-2):99-104
The separation of alkali metal (Li+, Na+, K+, Rb+ and Cs+) and ammonium cations on a C18 reversed-phase column using three anionic surfactants [sodium 1-eicosyl sulphate, sodium dodecyl benzenesulphonate and sodium dodecyl sulphate (SDS)] is described. Two methods were examined: (a) “permanent” coating, with the use of a C18 reversed-phase column previously coated with the surfactants; and (b) dynamic coating, with addition of the surfactants to the mobile phase. With method (a) the separation of the six cations was achieved with SDS. However, the retention times gradually decreased owing to dissolution of the SDS coating. Good separation was obtained with method (b), where 10 mM HNO3 containing 0.1 mM SDS was used as the mobile phase with conductivity detection, and it was applied satisfactorily to real samples. The effect of system peaks on determination is also discussed. 相似文献
978.
Hara M Samori S Cai X Tojo S Arai T Momotake A Hayakawa J Uda M Kawai K Endo M Fujitsuka M Majima T 《The journal of physical chemistry. B》2005,109(2):973-976
Formation and decay processes of stilbene core radical cation (ST*+) during the photoinduced electron transfer have been studied for a series of stilbene bearing benzyl ether-type dendrons (D). ST*+ and the radical cation of peripheral dendron (D*+) were generated by intermolecular hole transfer from biphenyl radical cation, which was generated from photoinduced electron transfer from biphenyl to the singlet-excited 9,10-dicyanoanthracene in a mixture of acetonitrile and 1,2-dichloroethane (3:1). An intramolecular dimer radical cation of benzyl groups at the terminal of stilbene dendrimer was indicated as a hole trapping site. Subsequent hole transfer from the trapping site to the core ST generated ST*+. The shielding effects of D depending on the dendrimer generation on the growth and decay of ST*+ were observed. It was revealed for the first time that D acts as the hole trapping site and the hole conductor on the way of the exothermic hole transfer from the terminal of D to the central core ST. We also found that D inhibits the charge recombination with 9,10-dicyanoanthracene radical anion because of the steric hindrance. 相似文献
979.
A new fluorescent chelator Oxa, having two metal-binding sites, was designed and synthesized in six steps. Oxa exhibited two distinctive dissociation constants for Zn2+ ( μM and μM), with considerable fluorescence increase in aqueous buffer at pH 7.2. Affinities of Oxa for the other biologically important ions such as Ca2+ ( μM and mM) and Mg2+ ( μM and could not be determined) in the same conditions were also obtained. 相似文献
980.
The first direct generation of synthetically useful alpha-phosphonovinyl radicals was achieved by treatment of alpha-phosphonovinyl halides with a tributyltin radical. The alpha-phosphonovinyl radicals 2a-d were trapped with electron-rich olefins and an electron-deficient olefin to produce alpha-functionalized vinylphosphonates 3a-f in 16-55% yields. The alpha-phosphonovinyl radicals 7e-g containing the YCH2CH=CH2 (Y = O, CH2, S) substituent at the beta-position afforded mixtures of 5-exo and 6-endo cyclization products, 5e-g and 6e-g, in good yields. The 5-exo/6-endo product ratios increase in the following order of the beta-substituent: OCH2CH=CH2 > CH2CH2CH=CH2 > SCH2CH=CH2. The effects of the beta-substituents upon the cyclization reaction were discussed. Radical cyclization of alpha-phosphonovinyl radicals bearing functional groups such as geranyloxy, geranylthio, and (2-cyclohexen-1-yl)thio groups at the beta-position afforded 5-exo, 5-exo and 6-endo, and cis-fused-5,6-ring cyclization products incorporating an alpha,beta-unsaturated phosphonate unit within the ring, respectively, in good yields. The alpha-phosphonovinyl radical 20 underwent tandem radical cyclization-radical cyclization to produce a mixture of two isomeric bicyclo[4.3.0]nonenes including a vinylphosphonate moiety in high yield. 相似文献